Fabric treating composition containing beta-cyclodextrin and essentially free of perfume

ABSTRACT

The present invention relates to a stable, aqueous odor-absorbing composition for use on inanimate surfaces. The composition comprises from about 0.1% to about 5% of solubilized, uncomplexed cyclodextrin, preferably, an effective amount of a solubilized, water-soluble antimicrobial preservative having a water-solubility of greater than about 0.3%, preferably, from about 0% to about 10%, by weight of the composition, of solubilized, water-soluble metallic salt, aqueous carrier and wherein said composition is essentially free of any material that would soil or stain fabric and wherein said composition is essentially free of perfume and has a pH of greater than about 3.

TECHNICAL FIELD

The present invention relates to a stable, preferably clear, aqueousodor-absorbing composition preferably not for use on human skin,comprising solubilized, uncomplexed cyclodextrin and optionally but,preferably, solubilized, water-soluble, antimicrobial preservative forsaid cyclodextrin solution and wherein said composition is essentiallyfree of perfume. The odor-absorbing composition is designed to controlodors caused by a broad spectrum of organic odoriferous materials, whichmay, or may not, contain reactive functional groups, and to remain shelfstable for a substantial period of time. Preferably, the aqueousodor-absorbing composition is for use on surfaces, especially fabrics,and more specifically, clothes, in order to restore and/or maintainfreshness by reducing malodor without the need for washing or drycleaning.

BACKGROUND OF THE INVENTION

The present invention relates to a stable, preferably clear, aqueousodor absorbing composition, preferably, not for use directly on humanskin, as an odor freshening composition. Preferably, the composition issprayed onto fabrics, particularly clothes, to restore their freshnessby reducing malodor, without washing or dry cleaning. The composition ispreferably not used directly on human skin because when the preferablepreservative is used it may cause skin irritation.

A wide variety of deodorizing compositions are known in the art, themost common of which contain perfumes to mask malodor. Odor masking isthe intentional concealment of one odor by the addition of another. Thecontrol of odor on fabrics, in particular clothes, has been accomplishedby using perfumes, colognes, etc. However, preference for perfume isgreatly varied and high levels are needed to ensure that the malodor isno longer noticeable.

Odor modification, in which the odor is changed, e.g., by chemicalmodification, has also been used. Current malodor modification methodsknown in the art are oxidative degradation, which uses oxidizing agentssuch as oxygen bleaches, chlorine, chlorinated materials such as sodiumhypochlorite, chlorine dioxide, etc., and potassium permanganate toreduce malodor, and reductive degradation which uses reducing agentssuch as sodium bisulfite to reduce malodor. Both of these methods areunacceptable for general use on fabric because they can damage coloredfabrics, specifically, they can bleach and discolor colored fabrics.

Other methods of odor control involve actives that are targeted to reactwith malodors having specific chemical functional groups. Examples ofsuch actives are; biguanide polymers, which complex with organiccompounds containing organically bound N and/or S atoms, and fattyalcohol esters of methyl methacrylic acid which react with thiols,amines, and aldehydes. Such actives are limited in scope because theyonly react with limited types of malodor. A more detailed description ofthese methods can be found in U.S. Pat. Nos. 2,544,093, 3,074,891,4,818,524, and 4,946,672, and U.K. Pat. App. No. 941,105, all of saidpatents and applications are incorporated herein by reference.

Other types of deodorizing compositions known in the art containantibacterial and antifungal agents which regulate the malodor producingmicroorganisms found on the surface to which the deodorizing compositionis directed. Many skin deodorant products use this technology. Thesecompositions are not effective on realodors that have already beenproduced and realodors that do not come from bacterial sources, such astobacco or food odors.

Fabric malodor is most commonly caused by environmental odors such astobacco odor, cooking and/or food odors, or body odor. The unpleasantodors are mainly organic molecules which have different structures andfunctional groups, such as amines, acids, alcohols, aldehydes, ketones,phenolics, polycyclics, indoles, aromatics, polyaromatics, etc. They canalso be made up of sulfur-containing functional groups, such as, thiol,mercaptan, sulfide and/or disulfide groups.

It is preferable to apply an odor absorbing material, preferably a broadspectrum odor absorbing material, to fabrics rather than a masking orchemical reaction material for odor control between washing and drycleaning operations. As opposed to a masking or chemical reactionmaterial, an odor absorbing material can eliminate a broad spectrum ofodoriferous molecules and usually does not contribute an odor of itsown. The commonly known solid odor absorbers such as activated charcoaland zeolites can be harmful to fabrics and therefore are not preferredas an odor controlling agent under these circumstances. Activatedcharcoal easily stains light colored fabrics and zeolites are seen as alight colored stain on dark colored fabrics.

Uncomplexed cyclodextrin molecules, which are made up of varying numbersof glucose units provide the absorbing advantages of known absorbentdeodorizing compositions without harmful effects to fabrics. The currentteachings in the art suggest that cyclodextrin does not contribute tothe growth of microorganisms despite the fact that they are made up ofvarying numbers of glucose units. See Effect ofHydroxypropyl-B-cyclodextrin on the Antimicrobial Action ofPreservatives, S. J. Lehner, B. W. Maller and J. K. Seydel, J. Pharm.Pharmacol 1994, 46:p.188 and Interactions Between P-Hydroxybenzoic acidEsters and Hydroxypropyl-B-Cyclodextrin and Their Antimicrobial EffectAgainst Candida Albicans, S. J. Lehner, B. W. Muller and J. K. Seydel,International Journal of Pharmaceutics, 1993, 93, pp. 201-208. It hasbeen discovered, however, that cyclodextrin is a prime breeding groundfor certain microorganisms, especially when in aqueous compositions.This growth problem leads to a problem with storage stability ofcyclodextrin solutions for any significant length of time. Contaminationby certain microorganisms, can cause microbial growth resulting in anunsightly and/or malodorous solution. Because microbial growth incyclodextrin solutions can occur, it is preferable to include awater-soluble antimicrobial preservative, which is effective forinhibiting and/or regulating microbial growth, to increase storagestability of clear, aqueous odor-absorbing solutions containingwater-soluble cyclodextrin.

SUMMARY OF THE INVENTION

The present invention relates to a stable, aqueous odor-absorbingcomposition for use on inanimate surfaces, comprising:

A. from about 0.1% to about 5% of solubilized, uncomplexed cyclodextrincomprising an effective amount of beta-cyclodextrin; and

B. preferably, an effective amount of a solubilized, water-solubleantimicrobial preservative having a water-solubility of greater thanabout 0.3%;

C. preferably, from about 0% to about 10%, by weight of the composition,of solubilized, water-soluble metallic salt; and

D. aqueous carrier; and

wherein said composition is essentially free of any material that wouldsoil or stain fabric; and wherein said composition is essentially freeof perfume and has a pH of greater than about 3.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a clear, aqueous odor-absorbingcomposition for use on inanimate surfaces, comprising

A. from about 0.1% to about 5% of solubilized, uncomplexed cyclodextrincomprising an effective amount of beta-cyclodextrin; and

B. preferably, an effective amount of a solubilized, water-solubleantimicrobial preservative having a water-solubility of greater thanabout 0.3%;

C. preferably, from about 0% to about 10%, by weight of the composition,of solubilized, water-soluble metallic salt; and

D. aqueous carrier; and

wherein said composition is essentially free of any material that wouldsoil or stain fabric; and wherein said composition is essentially freeof perfume and has a pH of greater than about 3.

I. COMPOSITION (A) CYCLODEXTRIN

As used herein, the term "cyclodextrin" includes any of the knowncyclodextrins such as unsubstituted cyclodextrins containing from six totwelve glucose units, especially, alpha-cyclodextrin, beta-cyclodextrin,gamma-cyclodextrin and/or their derivatives and/or mixtures thereof, solong as there is an effective amount of beta-cyclodextrin. Thealpha-cyclodextrin consists of six glucose units, the betacyclodextrinconsists of seven glucose units, and the gamma-cyclodextrin consists ofeight glucose units arranged in a donut-shaped ring. The specificcoupling and conformation of the glucose units give the cyclodextrins arigid, conical molecular structure with a hollow interior of a specificvolume. The "lining" of the internal cavity is formed by hydrogen atomsand glycosidic bridging oxygen atoms; therefore, this surface is fairlyhydrophobic. The unique shape and physical-chemical properties of thecavity enable the cyclodextrin molecules to absorb (form inclusioncomplexes with) organic molecules or parts of organic molecules whichcan fit into the cavity. Many odorous molecules can fit into the cavityincluding many malodorous molecules and perfume molecules. Therefore,cyclodextrins, and especially mixtures of cyciodextrins with differentsize cavities, can be used to control odors caused by a broad spectrumof organic odoriferous materials, which may or may not contain reactivefunctional groups. The complexation between cyclodextrin and odorousmolecules occurs rapidly in the presence of water. However, the extentof the complex formation also depends on the polarity of the absorbedmolecules. In an aqueous solution, strongly hydrophilic molecules (thosewhich are highly water-soluble) are only partially absorbed if at all.Therefore, cyclodextrin does not complex effectively with some very lowmolecular weight organic amines and acids when they are present at lowlevels on wet fabrics. As the water is being removed however, e.g., thefabric is being dried off, some low molecular weight organic amines andacids have more affinity and will complex with the cyclodextrins morereadily.

The cavities within the cyclodextrin in the solution of the presentinvention should remain essentially untilled (the cyclodextrin remainsuncomplexed) while in solution, in order to allow the cyclodextrin toabsorb various odor molecules when the solution is applied to a surface.The availability of solubilized, uncomplexed cyclodextrin is essentialfor effective and efficient odor control performance.

The individual cyclodextrins can also be linked together, e.g., usingmultifunctional agents to form oligomers, polymers, etc. Examples ofsuch materials are available commercially from Amaizo and from AldrichChemical Company (betacyclodextrin/epichlorohydrin copolymers).

Examples of highly water soluble cyclodextrins are, alpha-cyclodextrinand its derivatives thereof, gamma-cyclodextrin and its derivativesthereof, derivitised betacyclodextrin, and mixtures thereof Mixtures ofbeta-cyclodextrin and highly water-soluble cyclodextrins are alsopreferred.

Highly water-soluble cyciodextrins are those having a water-solubilityof at least about 10 g in 100 ml of water at room temperature,preferably at least about 20 g in 100 ml of water, more preferably atleast about 25 g in 100 ml of water at room temperature. Highlywater-soluble cyclodextrin derivatives include, e.g., those with shortchain alkyl groups such as methylated cyclodextrins, and ethylatedcyclodextrins, wherein R is a methyl or an ethyl group; those withhydroxyl substituted groups, such as hydroxypropyl cyclodextrins andhydroxyethyl cyclodextrins, wherein R is a CH₂ --CH(OH)--CH₃ or a CH₂CH₂ --OH groups; branched cyclodextrins such as maltose-bondedcyclodextrins; cationic cyclodextrins such as those containing2-hydroxy-3(dimethylamino)propyl ether, wherein R is CH₂ --CH(OH)--CH₂--N(CH₃)₂ ; quaternary ammonium, e.g.,2-hydroxy-3-(trimethylammonio)propyl ether chloride groups, wherein R isCH₂ --CH(OH)--CH₂ --N(CH₃)₃ Cl; anionic cyclodextrins such ascarboxymethyl cyclodextrins, cyclodextrin sulfates, and cyclodextrinsuccinylates; amphoteric cyclodextrins such as carboxymethyl/quaternaryammonium cyclodextrins; cyclodextrins wherein at least one glucopyranoseunit has a 3-6-anhydro-cyclomalto structure, e.g., themono-3-6-anhydrocyclodextrins, as disclosed in "Optimal Performanceswith Minimal Chemical Modification of Cyclodextrins", F. Diedaini-Pilardand B. Perly, The 7th International Cyclodextrin Symposium Abstracts,April 1994, p. 49, herein incorporated by reference; and mixturesthereof. Other cyclodextrin derivatives are disclosed in U.S. Pat. Nos:3,426,011, Parmerter et al., issued Feb. 4, 1969; 3,453,257, 3,453,258,3,453,259, and 3,453,260, all in the names of Parmerter et al., and allissued Jul. 1, 1969; 3,459,731, Gramera et al., issued Aug. 5, 1969;3,553,191, Parmerter et al., issued Jan. 5, 1971; 3,565,887, Parmerteret al., issued Feb. 23, 1971; 4,535,152, Szejtli et al., issued Aug. 13,1985; 4,616,008, Hirai et al., issued Oct. 7, 1986; 4,638,058, Brandt etal., issued Jan. 20, 1987; 4,746,734, Tsuchiyama et al., issued May 24,1988; and 4,678,598, Ogino et al., issued Jul. 7, 1987, all of saidpatents being incorporated herein by reference.

Examples of preferred water-soluble cyclodextrin derivatives suitablefor use herein are hydroxypropyl alpha-cyclodextrin, methylatedalpha-cyclodextrin, methylated beta-cyclodextrin, hydroxyethylbeta-cyclodextrin, and hydroxypropyl betacyclodextrin. hydroxyalkylcyclodextrin derivatives preferably have a degree of substitution offrom about 1 to about 14, more preferably from about 1.5 to about 7,wherein the total number of OR groups per cyclodextrin is defined as thedegree of substitution. Methylated cyclodextrin derivatives typicallyhave a degree of substitution of from about 1 to about 18, preferablyfrom about 3 to about 16. A known methylated beta-cyclodextrin isheptakis-2,6-di-O-methyl-β-cyclodextrin, commonly known as DIMEB, inwhich each glucose unit has about 2 methyl groups with a degree ofsubstitution of about 14. A preferred, more commercially availablemethylated beta-cyclodextrin is a randomly methylated beta-cyclodextrinhaving a degree of substitution of about 12.6. The preferredcyclodextrins are available, e.g., from American Maize-Products Companyand Wacker Chemicals (USA), Inc.

It is also preferable to use a mixture of cyclodextrins. Such mixturesabsorb odors more broadly by complexing with a wider range ofodoriferous molecules. Preferably at least a portion of thecyclodextrins are alpha-cyclodextrins, betacyclodextrins,gamma-cyclodextrins, and/or their derivatives. More preferably a mixtureof alpha-cyclodextrins, beta-cyclodextrins, and/or their derivatives,even more preferably a mixture of hydroxypropyl alpha-cyclodextrin andhydroxypropyl betacyclodextrin and/or a mixture of methylatedalpha-cyclodextrin and methylated betacyclodextrin.

Normal or non-derivitised beta-cyclodextrin which has a low watersolubility can be used up to a level of about 1.85%, which is its watersolubility at room temperature. In order to obtain the preferably clearsolution of the present invention it is essential that the compositionbe essentially free of perfume. Not to be limited by theory, it isbelieved that some beta-cyclodextrin and/or beta-cyclodextrin/perfumecomplexes solidify and/or precipitate out producing an undesirablecloudy aqueous solution.

Preferably, the odor absorbing solution of the present invention isclear. The term "clear" as defined herein means transparent ortranslucent, preferably transparent as in "water clear," when observedthrough a layer having a thickness of less than about 10 cm.

For controlling odor on fabrics, the composition is preferably used as aspray. It is preferable that the composition of the present inventioncontain low levels of cyclodextrin so that a visible stain does notappear on the fabric at normal usage levels. Typical levels ofcyclodextrin are from about 0.1% to about 5%, preferably from about 0.2%to about 4%, more preferably from about 0.3% to about 3%, mostpreferably from about 0.5% to about 2%. Compositions with higherconcentrations can leave unacceptable visible stains on fabrics as thesolution evaporates off of the fabric. This is especially a problem onthin, colored, synthetic fabrics. In order to avoid or minimize theoccurrence of fabric staining, it is preferable that the fabric betreated at a level of less than about 5 mg of cyclodextrin per mg offabric, more preferably less than about 2 mg of cyclodextrin per mg offabric.

Concentrated compositions can also be used in order to provide a lessexpensive product. When a concentration is used, i.e., when the level ofcyclodextrin used is from about 3% to about 5%, it is preferable todilute the composition before treating fabrics in order to avoidstaining. Preferably the cyclodextrin is diluted with about 50% to about2000%, more preferably with about 60% to about 1000%, most preferablywith about 75% to about 500% by weight of the composition of water.

(B) OPTIONAL ANTIMICROBIAL PRESERVATIVE

Optionally, but preferably, the composition of the present invention cancontain solubilized, water-soluble, antimicrobial preservative becausecyclodextrin molecules are made up of varying numbers of glucose unitswhich can make them a prime breeding ground for certain microorganisms,especially when in aqueous compositions. This problem, that certainorganisms grow extremely well on cyclodextrin, has not been previouslydisclosed. This drawback can lead to the problem of storage stability ofcyclodextrin solutions for any significant length of time. Contaminationby certain microorganisms with subsequent microbial growth can result inan unsightly and/or malodorous solution. Because microbial growth incyclodextrin solutions is highly objectionable when it occurs, it ispreferable to include a water-soluble, antimicrobial preservative, whichis effective for inhibiting and/or regulating microbial growth in orderto increase storage stability of the preferably clear, aqueousodor-absorbing solution containing water-soluble cyclodextrin.

Typical microorganisms that can be found in cyclodextrin supplies andwhose growth are found in the presence of cyclodextrin in aqueouscyclodextrin solutions include bacteria, e.g., Bacillus thuringiensis.(cereus group) and Bacillus sphaericus; and fungi, e.g., Aspergillusustus. Bacillus sphaericus is one of the most numerous members ofBacillus species in soils. Aspergillus ustus is common in grains andflours which are raw materials to produce cyclodextrins. Microorganismssuch as Escherichia coli and Pseudomonas aeruginosa are found in somewater sources, and can be introduced during the preparation ofcyclodextrin aqueous solutions.

It is preferable to use a broad spectrum preservative, e.g., one that iseffective on both bacteria (both gram positive and gram negative) andfungi. A limited spectrum preservative, e.g., one that is only effectiveon a single group of microorganisms, e.g., fungi, can be used incombination with a broad spectrum preservative or other limited spectrumpreservatives with complimentary activity. A mixture of broad spectrumpreservatives can also be used.

Antimicrobial preservatives useful in the present invention includebiocidal compounds, i.e., substances that kill microorganisms, orbiostatic compounds, i.e., substances that inhibit and/or regulate thegrowth of microorganisms.

Preferred antimicrobial preservatives are those that are water-solubleand are effective at low levels because the organic preservatives canform inclusion complexes with the cyclodextrin molecules and competewith the malodorous molecules for the cyclodextrin cavities, thusrendering the cyclodextrins ineffective as odor controlling actives.Water-soluble preservatives useful in the present invention are thosethat have a solubility in water of at least about 0.3 g per 100 ml ofwater, i.e., greater than about 0.3% at room temperature, preferablygreater than about 0.5% at room temperature. These types ofpreservatives have a lower affinity to the cyclodextrin cavity, at leastin the aqueous phase, and are therefore more available to provideantimicrobial activity. Preservatives with a water-solubility of lessthan about 0.3% and a molecular structure that readily fits into thecyclodextrin cavity, have a greater tendency to form inclusion complexeswith the cyclodextrin molecules, thus rendering the preservative lesseffective to control microbes in the cyclodextrin solution. Therefore,many well known preservatives such as short chain alkyl esters ofp-hydroxybenzoic acid, commonly known as parabens;N-(4-chlorophenyl)-N'-(3,4-dichlorophenyl) urea, also known as 3,4,4'-trichlorocarbanilide or triclocarban; 2,4,4'-trichloro-2'-hydroxydiphenyl ether, commonly known as triclosan are not preferred in thepresent invention since they are relatively ineffective when used inconjunction with cyclodextrin.

The water-soluble antimicrobial preservative in the present invention isincluded at an effective amount. The term "effective amount" as hereindefined means a level sufficient to prevent spoilage, or prevent growthof inadvertently added microorganisms, for a specific period of time. Inother words, the preservative is not being used to kill microorganismson the surface onto which the composition is deposited in order toeliminate odors produced by microorganisms. Instead, it is preferablybeing used to prevent spoilage of the cyclodextrin solution in order toincrease the shelf-life of the composition. Preferred levels ofpreservative are from about 0.0001% to about 0.5%, more preferably fromabout 0.0002% to about 0.2%, most preferably from about 0.0003% to about0.1%, by weight of the composition.

In order to reserve most of the cyclodextrins for odor control, thecyclodextrin to preservative mole ratio should be greater than about5:1, preferably greater than about 10:1, more preferably greater thanabout 50:1, even more preferably greater than about 100:1.

The preservative can be an organic material, which will not cause damageto fabric appearance, e.g., discoloration, coloration, bleaching.Preferred water-soluble preservatives include organic sulfur compounds,halogenated compounds, cyclic organic nitrogen compounds, low molecularweight aldehydes, quaternary ammonium compounds, dehydroacetic acid,phenyl and phenoxy compounds, and mixtures thereof.

The following are non-limiting examples of preferred water-solublepreservatives for use in the present invention.

(1) Organic Sulfur Compounds

Preferred water-soluble preservatives for use in the present inventionare organic sulfur compounds. Some non-limiting examples of organicsulfur compounds suitable for use in the present invention are:

(a) 3-Isothiazolone Compounds

A preferred preservative is an antimicrobial, organic preservativecontaining 3-isothiazolone groups having the formula: ##STR1## wherein

Y is an unsubstituted alkyl, alkenyl, or alkynyl group of from about 1to about 18 carbon atoms, an unsubstituted or substituted cycloalkylgroup having from about a 3 to about a 6 carbon ring and up to 12 carbonatoms, an unsubstituted or substituted aralkyl group of up to about 10carbon atoms, or an unsubstituted or substituted aryl group of up toabout 10 carbon atoms;

R¹ is hydrogen, halogen, or a (C₁ -C₄) alkyl group; and

R² is hydrogen, halogen, or a (C₁ -C₄) alkyl group.

Preferably, when Y is methyl or ethyl, R¹ and R² should not both behydrogen. Salts of these compounds formed by reacting the compound withacids such as hydrochloric, nitric, sulfuric, etc. are also suitable.

This class of compounds is disclosed in U.S. Pat. No. 4,265,899, Lewiset al., issued May 5, 1981, and incorporated herein by reference.Examples of said compounds are: 5-chloro-2-methyl-4-isothiazolin-3-one;2-n-butyl-3-isothiazolone; 2-benzyl-3-isothiazolone;2-phenyl-3-isothiazolone, 2-methyl-4,5-dichloroisothiazolone;5-chloro-2-methyl-3-isothiazolone; 2-methyl-4-isothiazolin-3-one; andmixtures thereof. A preferred preservative is a water-soluble mixture of5-chloro-2-methyl-4-isothiazolin-3-one and2-methyl-4-isothiazolin-3-one, more preferably a mixture of about 77%5-chloro-2-methyl-4-isothiazolin-3-one and about 23%2-methyl-4-isothiazolin-3-one, a broad spectrum preservative availableas a 1.5% aqueous solution under the tradename Kathon® CG by Rohm andHaas Company.

When Kathon® is used as the preservative in the present invention it ispresent at a level of from about 0.0001% to about 0.01%, preferably fromabout 0.0002% to about 0.005%, more preferably from about 0.0003% toabout 0.003%, most preferably from about 0.0004% to about 0.002%, byweight of the composition.

(b) Sodium Pyrithione

Another preferred organic sulfur preservative is sodium pyrithione, withwater solubility of about 50%. When sodium pyrithione is used as thepreservative in the present invention it is present at a level of fromabout 0.0001% to about 0.01%, preferably from about 0.0002% to about0.005%, more preferably from about 0.0003% to about 0.003%, by weight ofthe composition.

Mixtures of the preferred organic sulfur compounds can also be used asthe preservative in the present invention.

(2) Halogenated Compounds

Preferred preservatives for use in the present invention are halogenatedcompounds. Some non-limiting examples of halogenated compounds suitablefor use in the present invention are:

5-bromo-5-nitro-1,3-dioxane, available under the trade name Bronidox L®from Henkel. Bronidox L® has a solubility of about 0.46% in water. WhenBronidox is used as the preservative in the present invention it ispresent at a level of from about 0.0005% to about 0.02%, preferably fromabout 0.001% to about 0.01%, by weight of the composition;

2-bromo-2-nitropropane-1,3-diol, available under the trade name Bronopolfrom Inolex can be used as the preservative in the present invention.Bronopol has a solubility of about 25% in water. When Bronopol is usedas the preservative in the present invention it is present at a level offrom about 0.002% to about 0.1%, preferably from about 0.005% to about0.05%, by weight of the composition;

1,1'-hexamethylene bis(5-(p-chlorophenyl)biguanide), commonly known aschlorhexidine, and its salts, e.g., with acetic and digluconic acids canbe used as a preservative in the present invention. The digluconate saltis highly water-soluble, about 70% in water, and the diacetate salt hasa solubility of about 1.8% in water. When chlorohexidine is used as thepreservative in the present invention it is present at a level of fromabout 0.0001% to about 0.04%, preferably from about 0.0005% to about0.01%, by weight of the composition.

1,1,1-Trichloro-2-methylpropan-2-ol, commonly known as chlorobutanol,with water solubility of about 0.8%; typical effective level ofchlorobutanol is from about 0.1% to about 0.5%, by weight of thecomposition.

4,4'- (Trimethylenedioxy)bis-(3-bromobenzamidine) diisethionate, ordibromopropamidine, with water solubility of about 50%; whendibromopropamidine is used as the preservative in the present inventionit is present at a level of from about 0.0001% to about 0.05%,preferably from about 0.0005% to about 0.01% by weight of thecomposition.

Mixtures of the preferred halogenated compounds can also be used as thepreservative in the present invention.

(3) Cyclic Organic Nitrogen Compounds

Preferred water-soluble preservatives for use in the present inventionare cyclic organic nitrogen compounds. Some non-limiting examples ofcyclic organic nitrogen compounds suitable for use in the presentinvention are:

(a) Imidazolidinedione Compounds

Preferred preservatives for use in the present invention areimidazolidione compounds. Some non-limiting examples ofimidazolidinedione compounds suitable for use in the present inventionare:

1,3-bis(hydroxymethyl)-5,5-dimethyl-2,4-imidazolidinedione, commonlyknown as dimethyloldimethylhydantoin, or DMDM hydantoin, available as,e.g., Glydant® from Lonza. DMDM hydantoin has a water solubility of morethan 50% in water, and is mainly effective on bacteria. When DMDMhydantoin is used, it is preferable that it be used in combination witha broad spectrum preservative such as Kathon CG®, or formaldehyde. Apreferred mixture is about a 95:5 DMDM hydantoin to3-butyl-2-iodopropynylcarbamate mixture, available under the trade nameGlydant Plus® from Lonza. When Glydant Plus® is used as the preservativein the present invention, it is present at a level of from about 0.005%to about 0.2%;

N-[1,3-bis(hydroxymethyl)2,5-dioxo-4-imidazolidinyl]-N,N'bis(hydroxymethyl)urea, commonly known as diazolidinyl urea, available under the tradename Germall II® from Sutton Laboratories, Inc. (Sutton) can be used asthe preservative in the present invention. When Germall II® is used asthe preservative in the present invention, it is present at a level offrom about 0.01% to about 0.1%;

N,N"-methylenebis{N'-[1-(hydroxymethyl)-2,5-dioxo-4-imidazolidinyl]urea},commonly known as imidazolidinyl urea, available, e.g., under the tradename Abiol® from 3 V-Sigma, Unicide U-13® from Induchem, Germall 115®from (Sutton) can be used as the preservative in the present invention.When imidazolidinyl urea is used as the preservative, it is present at alevel of from about 0.05% to about 0.2%, by weight of the composition.

Mixtures of the preferred imidazolidinedione compounds can also be usedas the preservative in the present invention.

(b) Polymethoxy Bicyclic Oxazolidine

Another preferred water-soluble cyclic organic nitrogen preservative ispolymethoxy bicyclic oxazolidine, having the general formula: ##STR2##where n has a value of from about 0 to about 5, and is available underthe trade name Nuosept® C from Huls America. When Nuosept® C is used asthe preservative, it is present at a level of from about 0.005% to about0.1%, by weight of the composition.

Mixtures of the preferred cyclic organic nitrogen compounds can also beused as the preservative in the present invention.

(4) Low Molecular Weight Aldehydes (a) Formaldehyde

A preferred preservative for use in the present invention isformaldehyde. Formaldehyde is a broad spectrum preservative which isnormally available as formalin which is a 37% aqueous solution offormaldehyde. When formaldehyde is used as the preservative in thepresent invention, typical levels are from about 0.003% to about 0.2%,preferably from about 0.008% to about 0.1%. more preferably from about0.01% to about 0.05%, by weight of the composition.

(b) Glutaraldehyde

A preferred preservative for use in the present invention isglutaraldehyde. Glutaraldehyde is a water-soluble, broad spectrumpreservative commonly available as a 25% or a 50% solution in water.When glutaraldehyde is used as the preservative in the present inventionit is typically present at a level of from about 0.005% to about 0.1%,preferably from about 0.01% to about 0.05%, by weight of thecomposition.

(5) Quaternary Compounds

Preferred preservatives for use in the present invention are cationicand/or quaternary compounds. Such compounds include polyaminopropylbiguanide, also known as polyhexamethylene biguanide having the generalformula:

    HCl·NH.sub.2 --(CH.sub.2).sub.3 --[--(CH.sub.2).sub.3 --NH--C(=NH·HCl)--NH--(CH.sub.2).sub.3 --].sub.x --(CH.sub.2).sub.3 --NH--C(=NH)--NH·CN

Polyaminopropyl biguanide is a water-soluble, broad spectrumpreservative which is available as a 20% aqueous solution availableunder the trade name Cosmocil CQ® from ICI Americas, Inc., or under thetrade name Mikrokill® from Brooks, Inc.

1-(3-Chlorallyl)-3,5,7-triaza-1-azoniaadamantane chloride, available,e.g., under the trade name Dowicil 200 from Dow Chemical, is aneffective quaternary ammonium preservative; it is freely soluble inwater; however, it has the tendency to discolor (yellow), therefore itis not highly preferred.

Mixtures of the preferred quaternary ammonium compounds can also be usedas the preservative in the present invention.

When quaternary ammonium compounds are used as the preservative in thepresent invention, they are typically present at a level of from about0.005% to about 0.2%, preferably from about 0.01% to about 0.1%, byweight of the composition.

(6) Dehydroacetic Acid

A preferred preservative for use in the present invention isdehydroacetic acid. Dehydroacetic acid is a broad spectrum preservativepreferably in the form of a sodium or a potassium salt so that it iswater-soluble. This preservative acts more as a biostatic preservativethan a biocidal preservative. When dehydroacteic acid is used as thepreservative it is typically used at a level of from about 0.005% toabout 0.2%, preferably from about 0.008% to about 0.1%, more preferablyfrom about 0.01% to about 0.05%, by weight of the composition.

(7) Phenyl and Phenoxy Compounds

Some non-limiting examples of phenyl and phenoxy compounds suitable foruse in the present invention are:

4,4'-diamidino-α,ω-diphenoxypropane diisethionate, commonly known aspropamidine isethionate, with water solubility of about 16%; and4,4'-diamidino-α,ω-diphenoxyhexane diisethionate, commonly known ashexamidine isethionate. Typical effective level of these salts is about0.0002% to about 0.05%.

Other examples are benzyl alcohol, with a water solubility of about 4%;2-phenylethanol, with a water solubility of about 2%; and2-phenoxyethanol, with a water solubility of about 2.67%; typicaleffective levels of these phenyl and phenoxy alcohols are from about0.1% to about 0.5%, by weight of the composition.

(8) Mixtures thereof

The preservatives of the present invention can be used in mixtures inorder to control a broad range of microorganisms.

Bacteriostatic effects can sometimes be obtained for aqueouscompositions by adjusting the composition pH to an acid pH, e.g., lessthan about pH 4, preferably less than about pH 3, or a basic pH, e.g.,greater than about 10, preferably greater than about 11. Low pH formicrobial control is not a preferred approach in the present inventionbecause the low pH can cause chemical degradation of the cyclodextrins.High pH for microbial control is also not preferred because at highpH's, e.g., greater than about 10, preferably greater than about 11, thecyclodextrins can be ionized and their ability to complex with organicmaterials is reduced. Therefore, aqueous compositions of the presentinvention should have a pit of from about 3 to about 10, preferably fromabout 4 to about 8, more preferably from about 4.5 to about 7.

As stated above, it is preferable to use the preservative at aneffective amount, as defined hereinabove. Optionally however, thepreservative can be used at a level which provides an antimicrobialeffect on the treated fabrics. Even when the preservative is used inthis capacity, it is preferable that an effective level of cyclodextrinmolecules remain uncomplexed in the solution in order to provide theodor absorbing benefit.

(C) CARRIER

Aqueous solutions are preferred for odor control. The dilute aqueoussolution provides the maximum separation of cyclodextrin molecules onthe fabric and thereby maximizes the chance that an odor molecule willinteract with a cyclodextrin molecule.

The preferred carrier of the present invention is water. The water whichis used can be distilled, deionized, or tap water. Water not only servesas the liquid carrier of the cyclodextrins, but it also facilitates thecomplexation reaction between the cyclodextrin molecules and themalodorous molecules. It has recently been discovered that water has anunexpected odor controlling effect of its own. It has been discoveredthat the intensity of the odor generated by some polar, low molecularweight organic amines, acids, and mercaptans is reduced when theodor-contaminated fabrics are treated with an aqueous solution. Not tobe bound by theory, it is believed that water solubilizes and depressesthe vapor pressure of these polar, low molecular weight organicmolecules, thus reducing their odor intensity.

(D) OPTIONAL INGREDIENTS

The composition of the present invention can optionally contain adjunctodor-controlling materials, chelating agents, solubilizing aids,antifoaming agents, defoaming agents, antistatic agents, insect and mothrepelling agents, colorants, especially blueing agents, antioxidants,and mixtures thereof. Incorporating adjunct odor-controlling materialscan enhance the capacity of the cyclodextrin to control odors as well asbroaden the range of odor types and molecule sizes which can becontrolled. Such materials include, for example, metallic salts,water-soluble cationic and anionic polymers, water-soluble bicarbonatesalts, zeolites, activated carbon, and mixtures thereof.

(1) Metallic Salt

Optionally, but highly preferred, the present invention can includemetallic salts for added odor absorption and/or antimicrobial benefitfor the cyclodextrin solution. The metallic salts are selected from thegroup consisting of copper salts, zinc salts, and mixtures thereof.

Copper salts have some antimicrobial benefits. Specifically, cupticabietate acts as a fungicide, copper acetate acts as a mildew inhibitor,cupric chloride acts as a fungicide, copper lactate acts as a fungicide,and copper sulfate acts as a germicide. Copper salts also possess somemalodor control abilities. See U.S. Pat. No. 3,172,817, Leupold, et al.,which discloses deodorizing compositions for treating disposablearticles, comprising at least slightly water-soluble salts ofacylacetone, including copper salts and zinc salts, all of said patentsincorporated herein by reference.

Zinc salts possess malodor control abilities. Zinc has been used mostoften for its ability to ameliorate malodor, e.g., in mouth washproducts, as disclosed in U.S. Pat. Nos. 4,325,939, issued Apr. 20, 1982and 4,469,674, issued Sep. 4, 1983, to N. B. Shah, et al., all of whichare incorporated herein by reference. Highly-ionized and soluble zincsalts such as zinc chloride, provide the best source of zinc ions. Zincborate functions as a fungistat and a mildew inhibitor, zinc caprylatefunctions as a fungicide, zinc chloride provides antiseptic anddeodorant benefits, zinc ricinoleate functions as a fungicide, zincsulfate heptahydrate functions as a fungicide and zinc undecylenatefunctions as a fungistat.

Preferably the metallic salts are water-soluble zinc salts, copper saltsor mixtures thereof, and more preferably the metallic salt is ZnCl₂.These salts are preferably present in the present invention primarily toabsorb amine and sulfur-containing compounds that have molecular sizestoo small to be effectively complexed with the cyclodextrin molecules.Low molecular weight sulfur-containing materials, e.g., sulfide andmercaptans, are components of many types of realodors, e.g., food odors(garlic, onion), body/perspiration odor, breath odor, etc. Low molecularweight amines are also components of many realodors, e.g., food odors,body odors, urine, etc.

When metallic salts are added to the composition of the presentinvention they are typically present at a level of from about 0.1% toabout 10%, preferably from about 0.2% to about 8%, more preferably fromabout 0.3% to about 5% by weight of the composition. When zinc salts areused as the metallic salt, and a clear solution is desired, it ispreferable that the pH of the solution is adjusted to less than about 7,more preferably less than about 6, most preferably less than about 5 inorder to keep the solution clear.

(2) Water-Soluble Polymers

Some water-soluble polymers, e.g., water-soluble cationic polymer andwater-soluble anionic polymers can be used in the composition of thepresent invention to provide additional odor control benefits.

a. Cationic Polymers, e.g., Polyamines

Water-soluble cationic polymers, e.g., those containing aminofunctionalities, amido functionalities, and mixtures thereof, such aspolyacrylamides, are useful in the present invention to control certainacid-type odors.

b. Anionic Polymers, e.g., Polyacrylic Acid

Water-soluble artionic polymers, e.g., polyacrylic acids and theirwater-soluble salts are useful in the present invention to controlcertain amine-type odors. Preferred polyacrylic acids and their alkalimetal salts have an average molecular weight of less than about 20,000,more preferably less than 5,000. Polymers containing sulfonic acidgroups, phosphoric acid groups, phosphonic acid groups, and theirwater-soluble salts, and mixtures thereof, and mixtures with carboxylicacid and carboxylate groups, are also suitable.

Water-soluble polymers containing both cationic and anionicfunctionalities are also suitable. Examples of these polymers are givenin U.S. Pat. 4,909,986, issued Mar. 20, 1990 to N. Kobayashi and A.Kawazoe, incorporated herein by reference. Another example ofwater-soluble polymers containing both cationic and anionicfunctionalities is a copolymer of dimethyldiallyl ammonium chloride andacrylic acid, commercially available under the trade name Merquat 280®from Calgon.

(3) Low Molecular Weight Polyols

Low molecular weight polyols with relatively high boiling points, ascompared to water, such as ethylene glycol, propylene glycol and/orglycerol are preferred optional ingredients for improving odor controlperformance of the composition of the present invention. Not to be boundby theory, it is believed that the incorporation of a small amount oflow molecular weight glycols into the composition of the presentinvention enhances the formation of the cyclodextrin inclusion complexesas the fabric dries.

It is believed that the polyols' ability to remain on the fabric for alonger period of time than water, as the fabric dries allows them toform ternary complexes with the cyclodextrin and some malodorousmolecules. The addition of the glycols is believed to fill up void spacein the cyclodextrin cavity that is unable to be filled by some malodormolecules of relatively smaller sizes. Preferably the glycol used isethylene glycol, and/or propylene glycol. Cyclodextrins prepared byprocesses that result in a level of such polyols are highly desirable,since they can be used without removal of the polyols.

When glycols are added to the composition of the present invention thepreferred weight ratio of low molecular weight polyol to cyclodextrin isfrom about 1:1,000 to about 20:100, more preferably from about 3:1,000to about 15:100, even more preferably from about 5:1,000 to about10:100, and most preferably from about 1:100 to about 7:100.

(4) Soluble Carbonate and Bicarbonate Salts

Water-soluble alkali metal carbonate and bicarbonate salts, such assodium bicarbonate, potassium bicarbonate, potassium carbonate, cesiumcarbonate, sodium carbonate, and mixtures thereof can be added to thecomposition of the present invention in order to help to control certainacid-type odors. Preferred salts are sodium carbonate monohydrate,potassium carbonate, sodium bicarbonate, potassium bicarbonate, andmixtures thereof. When these salts are added to the composition of thepresent invention, they are typically present at a level of from about0.1% to about 5%, preferably from about 0.2% to about 3%, morepreferably from about 0.3% to about 2%, by weight of the composition.When these salts are added to the composition of the present inventionit is preferably that incompatible metal salts not be present in theinvention. Preferably, when these salts are used the composition shouldbe essentially free of zinc and other incompatible metal ions, e.g., Ca,Fe, Ba, etc.

(5) Chelating Agents

Some amino acid chelating agents such as ethylene diamine tetraaceticacid (EDTA) can optionally be added to the composition of the presentinvention in order to enhance the activity of the water-soluble,antimicrobial preservative. When a chelating agent is added to thecomposition of the present invention, it is typically present at a levelof from about 0.01% to about 0.3%, preferably from about 0.05% to about0.2%. It is important that the composition of the present invention beessentially free of any metal ions that can be chelated by any chelatingagent that is added to the composition of the present invention becausesuch metal ions complex with, and deactivate, the chelating agents.

(6) Antistatic Agents

The composition of the present invention can optionally contain aneffective amount of antistatic agent to provide the treated clothes within-wear static. Preferred antistatic agents are those that are watersoluble in at least effective amount, such that the composition remainsa clear solution. Examples of these antistatic agents are monoalkylcationic quaternary ammonium compounds, e.g., mono(C₁₀ -C₁₄alkyl)trimethyl ammonium halide, such as monolauryl trimethyl ammoniumchloride, hydroxycetyl hydroxyethyl dimethyl ammonium chloride,available under the trade name Dehyquart E® from Henkel, and ethylbis(polyethoxy ethanol) alkylammonium ethylsulfate, available under thetrade name Variquat 66® from Witco Corp., polyethylene glycols,polymeric quaternary ammonium salts, such as polymers conforming to thegeneral formula:

--[N(CH₃)₂ --(CH₂)₃ --NH--CO--NH--(CH₂)₃ --N(CH₃)₂ ⁺ --CH₂ CH₂ OCH₂ CH₂]_(x) ²⁺ 2x[Cl--]

available under the trade name Mirapol A-15® from Rhone-Poulenc, and

--[N(CH₃)₂ --(CH₂)₃ --NH--CO--(CH₂)₄ --CO--NH--(CH₂ ₃ --N(CH₃)₂ --(CH₂CH₂ OCH₂ CH₂ ]_(x) ⁺ x[Cl--].

available under the trade name Mirapol AD-1® from Rhone-Poulenc,quaternized polyethyleneimines,vinylpyrrolidone/methacrylamidopropyltrimethylammonium chloridecopolymer, available under the trade name Gafquat HS-100® from GAF;triethonium hydrolyzed collagen ethosulfate, available under the tradename Quat-Pro E® from Maybrook; and mixtures thereof.

It is preferred that a no foaming or low foaming agent is used, to avoidfoam formation during fabric treatment. It is also preferred thatpolyethoxylated agents such as polyethylene glycol or Variquat 66® arenot used when alpha-cyclodextrin is used. The polyethoxylate groups havea strong affinity to and readily complex with alphacyclodextrin which inturn deplete the uncomplexed cyclodextrin available for odor control.

When an antistatic agent is used it is typically present at a level offrom about 0.05% to about 10%, preferably from about 0.1% to about 5%,more preferably from about 0.3% to about 3%, by weight of thecomposition.

(7) Insect and/or Moth Repelling Agent

The composition of the present invention can optionally contain aneffective amount of insect and/or moth repelling agents. Typical insectand moth repelling agents are pheromones, such as anti-aggregationpheromones, and other natural and/or synthetic ingredients. Preferredinsect and moth repellent agents useful in the composition of thepresent invention are perfume ingredients, such as citronellol,citranellal, citral, linalool, cedar extract, geranium oil, sandalwoodoil, 2-(diethylphenoxy)ethanol, etc. Other examples of insect and/ormoth repellents useful in the composition of the present invention aredisclosed in U.S. Pat. Nos. 4,449,987, 4,693,890, 4,696,676, 4,933,371,5,196,200, and in "Semio Activity of Flavor and Fragrance Molecules onVarious Insect Species", B. D. Mookherjee et al., published in BioactiveVolatile Compounds from Plants, ASC Symposium Series 525, R. Teranishi,R. G. Buttery, and H. Sugisawa, 1993, pp. 35-48, all of said patents andpublications being incorporated herein by reference. When an insectand/or moth repellent is used it is typically present at a level of fromabout 0.005% to about 3%, by weight of the composition.

(8) Solubilizing Aid

The odor absorbing composition of the present invention can alsooptionally contain a solubilizing aid to solubilize any excesshydrophobic organic materials, e.g., perfume, insect repelling agent,antioxidant, etc., that are not readily soluble in the composition, toform a clear solution. A suitable solubilizing aid is surfactant,preferably no-foaming or low-foaming surfactant. Suitable surfactantsare nonionic surfactants, anionic surfactants, cationic surfactants,amphoteric surfactants, zwitterionic surfactants, and mixtures thereof.Suitable surfactants can be emulsifiers and/or detersive surfactants.Mixtures of emulsifiers and detersive surfactants are also preferred.When a surfactant containing one, or more, aliphatic alkyl group isused, it is preferred that it contain relatively short alkyl chains offrom about 5 to about 14 carbon atoms. Preferred nonionic surfactantsare polyethylene glycol-polypropylene glycol block copolymers, such asPluronic® and Pluronic R® surfactants from BASF; Tetronic® and TetronicR® surfactants from BASF, ethoxylated branched aliphatic diols such asSurfynol® surfactants from Air Products; ethoxylated alkyl phenols, suchas Igepal® surfactants from Rhone-Poulenc; ethoxylated aliphaticalcohols and carboxylic acids; polyethylene glycol diesters of fattyacids; fatty acid esters of ethoxylated sorbitans; and mixtures thereof.Preferred anionic surfactants are dialkyl sulfosuccinate,alkylarylsulfonate, fatty alcohol sulfate, paraffin sulfonate, alkylsarcosinate, alkyl isethionate salts having suitable cations, e.g.,sodium, potassium, alkanol ammonium, etc., and mixtures thereof.Preferred amphoteric surfactants are the betaines. It is preferred thatthe surfactant have good wetting properties. Also preferred aresurfactants that have the hydrophilic groups situated betweenhydrophobic chains, such as Pluronic R® surfactants, Surfynolsurfactants, polyethylene glycol diesters of fatty acids, fatty acidesters of ethoxylated sorbitans, dialkyl sulfosuccinate, di(C₈ -C₁₂alkyl)di(C1-C2 alkyl)ammonium halides, and mixtures thereof; orsurfactants that have the hydrophobic chains situated betweenhydrophilic groups, such as Pluronic surfactants; and mixtures thereof.Mixtures of these surfactants and other types of surfactants are alsopreferred to form no-foaming or low-foaming solubilizing agents.Polyalkylene glycol can be used as a defoaming agent in combination withthe solubilizing agents.

If solubilizing agent is used in the present compositions, it istypically used at a level of from about 0.05% to about 1% by weight ofthe composition, more preferably from about 0.05% to about 0.3%.

(9) Additional Odor Absorbers

When the clarity of the solution is not needed, and the solution is notsprayed on fabrics, other optional odor absorbing materials, e.g.,zeolites and activated carbon, can also be used.

(a) Zeolites

A preferred class of zeolites is characterized as "intermediate"silicate/aluminate zeolites. The intermediate zeolites are characterizedby SiO₂ /AlO₂ molar ratios of less than about 10. Preferably the molarratio of SiO₂ /AlO₂ ranges from about 2 to about 10. The intermediatezeolites have an advantage over the "high" zeolites. The intermediatezeolites have a higher affinity for amine-type odors, they are moreweight efficient for odor absorption because they have a larger surfacearea, and they are more moisture tolerant and retain more of their odorabsorbing capacity in water than the high zeolites. A wide variety ofintermediate zeolites suitable for use herein are commercially availableas Valfor® CP301-68, Valfor® 300-63, Valfor® CP300-35, and Valfor®CP300-56, available from PQ Corporation, and the CBV100® series ofzeolites from Conteka.

Zeolite materials marketed under the trade name Abscents® andSmellrite®, available from The Union Carbide Corporation and UOP arealso preferred. These materials are typically available as a whitepowder in the 3-5 micron particle size range. Such materials arepreferred over the intermediate zeolites for control ofsulfur-containing odors, e.g., thiols, mercaptans.

(b) Activated Carbon

The carbon material suitable for use in the present invention is thematerial well known in commercial practice as an absorbent for organicmolecules and/or for air purification purposes. Often, such carbonmaterial is referred to as "activated" carbon or "activated" charcoal.Such carbon is available from commercial sources under such trade namesas; Calgon-Type CPG®; Type PCB®; Type SGL®; Type CAL®; and Type OL®.

It is preferred that no, or essentially no, volatile low molecularweight monohydric alcohols such as ethanol and/or isopropanol areintentionally added to the composition of the present invention sincethese volatile organic compounds will contribute both to flammabilityproblems and environmental pollution problems. If small amounts of lowmolecular weight monohydric alcohols are present in the composition ofthe present invention due to the addition of these alcohols to suchthings as perfumes and as stabilizers for some preservatives, it ispreferable that the level of monohydric alcohol be less than about 5%,preferably less than about 3%, more preferably less than about 1%.

(10) Colorant

Colorants and dyes, especially blueing agents, can be optionally addedto the odor absorbing compositions for visual appeal and performanceimpression. When colorants are used, they are used at extremely lowlevels to avoid fabric staining. Preferred colorants for use in thepresent compositions are highly water-soluble dyes, e.g., Liquitint®dyes available from Milliken Chemical Co. Non-limiting examples ofsuitable dyes are, Liquitint Blue HP®, Liquitint Blue 65®, LiquitintPatent Blue®, Liquitint Royal Blue®, Liquitint Experimental Yellow8949-43®, Liquitint Green HMC®, Liquitint Yellow II®, and mixturesthereof, preferably Liquitint Blue HP®, Liquitint Blue 65®, LiquitintPatent Blue®, Liquitint Royal Blue®, Liquitint Experimental Yellow8949-43®, and mixtures thereof.

(11) ARTICLE OF MANUFACTURE

The composition of the present invention can also be used in an articleof manufacture comprising said composition plus a spray dispenser. Whenthe commercial embodiment of the article of manufacture is used, it isoptional, but preferable, to include the preservative. Therefore, themost basic article of manufacture comprises uncomplexed cyclodextrin, acarrier, and a spray dispenser.

SPRAY DISPENSER

The article of manufacture herein comprises a spray dispenser. Thecyclodextrin composition is placed into a spray dispenser in order to bedistributed onto the fabric. Said spray dispenser is any of the manuallyactivated means for producing a spray of liquid droplets as is known inthe art, e.g. trigger-type, pump-type, non-aerosol self-pressurized, andaerosol-type spray means. The spray dispenser herein does not includethose that will substantially foam the clear, aqueous odor absorbingcomposition. It is preferred that at least about 80%, more preferably,at least about 90% of the droplets have a particle size of larger thanabout 30 μm.

The spray dispenser can be an aerosol dispenser. Said aerosol dispensercomprises a container which can be constructed of any of theconventional materials employed in fabricating aerosol containers. Thedispenser must be capable of withstanding internal pressure in the rangeof from about 20 to about 110 p.s.i.g., more preferably from about 20 toabout 70 p.s.i.g. The one important requirement concerning the dispenseris that it be provided with a valve member which will permit the clear,aqueous odor absorbing composition contained in the dispenser to bedispensed in the form of a spray of very fine, or finely divided,particles or droplets. The aerosol dispenser utilizes a pressurizedsealed container from which the clear, aqueous odor-absorbingcomposition is dispensed through a special actuator/valve assembly underpressure. The aerosol dispenser is pressurized by incorporating thereina gaseous component generally known as a propellant. Common aerosolpropellants, e.g., gaseous hydrocarbons such as isobutane, and mixedhalogenated hydrocarbons, are not preferred. Halogenated hydrocarbonpropellants such as chlorofluoro hydrocarbons have been alleged tocontribute to environmental problems. Hydrocarbon propellants can formcomplexes with the cyclodextrin molecules thereby reducing theavailability of uncomplexed cyclodextrin molecules for odor absorption.Preferred propellants are compressed air, nitrogen, inert gases, carbondioxide, etc. A more complete description of commercially availableaerosol-spray dispensers appears in U.S. Pat. Nos.: 3,436,772, Stebbins,issued Apr. 8, 1969; and 3,600,325, Kaufman et al., issued Aug. 17,1971; both of said references are incorporated herein by reference.

Preferably the spray dispenser can be a self-pressurized non-aerosolcontainer having a convoluted liner and an elastomeric sleeve. Saidself-pressurized dispenser comprises a liner/sleeve assembly containinga thin, flexible radially expandable convoluted plastic liner of fromabout 0.010 to about 0.020 inch thick, inside an essentially cylindricalelastomeric sleeve. The liner/sleeve is capable of holding a substantialquantity of odor-absorbing fluid product and of causing said product tobe dispensed. A more complete description of self-pressurized spraydispensers can be found in U.S. Pat. Nos. 5,111,971, Winer, issued May12, 1992, and 5,232,126, Winer, issued Aug. 3, 1993; both of saidreferences are herein incorporated by reference. Another type of aerosolspray dispenser is one wherein a barrier separates the odor absorbingcomposition from the propellant (preferably compressed air or nitrogen).Such a dispenser is available from EP Spray Systems, East Hanover, N.J.

More preferably, the spray dispenser is a non-aerosol, manuallyactivated, pump-spray dispenser. Said pump-spray dispenser comprises acontainer and a pump mechanism which securely screws or snaps onto thecontainer. The container comprises a vessel for containing the aqueousodor-absorbing composition to be dispensed.

The pump mechanism comprises a pump chamber of substantially fixedvolume, having an opening at the inner end thereof. Within the pumpchamber is located a pump stem having a piston on the end thereofdisposed for reciprocal motion in the pump chamber. The pump stem has apassageway there through with a dispensing outlet at the outer end ofthe passageway and an axial inlet port located inwardly thereof.

The container and the pump mechanism can be constructed of anyconventional material employed in fabricating pump-spray dispensers,including, but not limited to: polyethylene; polypropylene;polyethyleneterephthalate; blends of polyethylene, vinyl acetate, andrubber elastomer. A preferred container is made of clear, e.g.,polyethylene terephthalate. Other materials can include stainless steel.A more complete disclosure of commercially available dispensing devicesappears in: U.S. Pat. Nos.: 4,895,279, Schultz, issued Jan. 23, 1990;4,735,347, Schultz et al., issued Apr. 5, 1988; and 4,274,560, Carter,issued Jun. 23, 1981; all of said references are herein incorporated byreference.

Most preferably, the spray dispenser is a manually activatedtrigger-spray dispenser. Said trigger-spray dispenser comprises acontainer and a trigger both of which can be constructed of any of theconventional material employed in fabricating trigger-spray dispensers,including, but not limited to: polyethylene; polypropylene; polyacetal;polycarbonate; polyethyleneterephthalate; polyvinyl chloride;polystyrene; blends of polyethylene, vinyl acetate, and rubberelastomer. Other materials can include stainless steel and glass. Apreferred container is made of clear, e.g. polyethylene terephthalate.The trigger-spray dispenser does not incorporate a propellant gas intothe odor-absorbing composition, and preferably it does not include thosethat will foam the odor-absorbing composition. The trigger-spraydispenser herein is typically one which acts upon a discrete amount ofthe odor-absorbing composition itself, typically by means of a piston ora collapsing bellows that displaces the composition through a nozzle tocreate a spray of thin liquid. Said trigger-spray dispenser typicallycomprises a pump chamber having either a piston or bellows which ismovable through a limited stroke response to the trigger for varying thevolume of said pump chamber. This pump chamber or bellows chambercollects and holds the product for dispensing. The trigger spraydispenser typically has an outlet check valve for blocking communicationand flow of fluid through the nozzle and is responsive to the pressureinside the chamber. For the piston type trigger sprayers, as the triggeris compressed, it acts on the fluid in the chamber and the spring,increasing the pressure on the fluid. For the bellows spray dispenser,as the bellows is compressed, the pressure increases on the fluid. Theincrease in fluid pressure in either trigger spray dispenser acts toopen the top outlet check valve. The top valve allows the product to beforced through the swirl chamber and out the nozzle to form a dischargepattern. An adjustable nozzle cap can be used to vary the pattern of thefluid dispensed.

For the piston spray dispenser, as the trigger is released, the springacts on the piston to return it to its original position. For thebellows spray dispenser, the bellows acts as the spring to return to itsoriginal position. This action causes a vacuum in the chamber. Theresponding fluid acts to close the outlet valve while opening the inletvalve drawing product up to the chamber from the reservoir.

A more complete disclosure of commercially available dispensing devicesappears in U.S. Pat. Nos. 4,082,223, Nozawa, issued Apr. 4, 1978;4,161,288, McKinney, issued Jul. 17, 1985; 4,434,917, Saito et al.,issued Mar. 6, 1984; and 4,819,835, Tasaki, issued Apr. 11, 1989;5,303,867, Peterson, issued Apr. 19, 1994; all of said references areincorporated herein by reference.

A broad array of trigger sprayers or finger pump sprayers are suitablefor use with the compositions of this invention. These are readilyavailable from suppliers such as Calmar, Inc., City of Industry, Calif.;CSI (Continental Sprayers, Inc.), St. Peters, Mo.; Berry Plastics Corp.,Evansville, Indiana--a distributor of Guala® sprayers; or SeaquestDispensing, Cary, Ill.

The preferred trigger sprayers are the blue inserted Guala® sprayer,available from Berry Plastics Corp., or the Calmar TS800-1A sprayers,available from Calmar Inc., because of the fine uniform spraycharacteristics, spray volume, and pattern size. Any suitable bottle orcontainer can be used with the trigger sprayer, the preferred bottle isa 17 fl-oz. bottle (about 500 ml) of good ergonomics similar in shape tothe Cinch® bottle. It can be made of any materials such as high densitypolyethylene, polypropylene, polyvinyl chloride, polystyrene,polyethylene terephthalate, glass, or any other material that formsbottles. Preferably, it is made of high density polyethylene or clearpolyethylene terephthalate.

For smaller four fl-oz. size (about 118 ml), a finger pump can be usedwith canister or cylindrical bottle. The preferred pump for thisapplication is the cylindrical Euromist II® from Seaquest Dispensing.

III. METHOD OF USE

The cyclodextrin solution herein can be used by distributing, e.g., byplacing the aqueous solution into a dispensing means, preferably a spraydispenser and spraying an effective amount onto the desired surface orarticle. An effective amount as defined herein means an amountsufficient to absorb odor to the point that it is not discernible by thehuman sense of smell yet not so much as to saturate or create a pool ofliquid on said article or surface and so that when dry there is novisual deposit readily discernible. Distribution can be achieved byusing a spray device, a roller, a pad, etc.

Preferably, the present invention does not encompass distributing thecyclodextrin solution on to shiny surfaces including, e.g., chrome,glass, smooth vinyl, leather, shiny plastic, shiny wood, etc. It ispreferable not to distribute the cyclodextrin solution onto shinysurfaces because spotting and filming can more readily occur on thesurfaces. Furthermore, the cyclodextrin solution is not for use on humanskin, especially when an antimicrobial preservative is present in thecomposition because skin irritation can occur.

The present invention encompasses the method of spraying an effectiveamount of cyclodextrin solution onto household surfaces. Preferably saidhousehold surfaces are selected from the group consisting ofcountertops, cabinets, walls, floors, bathroom surfaces and kitchensurfaces.

The present invention encompasses the method of spraying a mist of aneffective amount of cyclodextrin solution onto fabric and/or fabricarticles. Preferably, said fabric and/or fabric articles include, butare not limited to, clothes, curtains, drapes, upholstered furniture,carpeting, bed linens, bath linens, tablecloths, sleeping bags, tents,car interior, etc.

The present invention encompasses the method of spraying a mist of aneffective amount of cyclodextrin solution onto and into shoes whereinsaid shoes are not sprayed to saturation.

The present invention encompasses the method of spraying a mist of aneffective amount of cyclodextrin solution onto shower curtains.

The present invention relates to the method of spraying a mist of aneffective amount of cyclodextrin solution onto and/or into garbage cansand/or recycling bins.

The present invention relates to the method of spraying a mist of aneffective amount of cyclodextrin solution into the air to absorbmalodor.

The present invention relates to the method of spraying a mist of aneffective amount of cyclodextrin solution into and/or onto majorhousehold appliances including but not limited to: refrigerators,freezers, washing machines, automatic dryers, ovens, microwave ovens,dishwashers etc., to absorb malodor.

The present invention relates to the method of spraying a mist of aneffective amount of cyclodextrin solution onto cat litter, pet beddingand pet houses to absorb malodor.

The present invention relates to the method of spraying a mist of aneffective amount of cyclodextrin solution onto household pets to absorbmalodor.

All percentages, ratios, and parts herein, in the Specification,Examples, and Claims are by weight and are approximations unlessotherwise stated.

The following are non-limiting examples of the instant composition.Perfume compositions that are used herein are as follows:

The following are non-limiting examples of the instant composition.

    ______________________________________                                                         Example I Example II                                         Ingredients      Wt. %     Wt. %                                              ______________________________________                                        beta-Cyclodextrin                                                                              1.0       0.5                                                alpha-Cyclodextrin                                                                             --        0.5                                                Kathon CG        0.001     0.0008                                             Distilled Water  Balance   Balance                                            ______________________________________                                    

Examples I and II

The ingredients of Examples I and lI are mixed and dissolved into clearsolutions.

    ______________________________________                                                          Example III                                                                              Example IV                                       Ingredients       Wt. %      Wt. %                                            ______________________________________                                        Methylated alpha-cyclodextrin                                                                   0.27       --                                               Methylated beta-cyclodextrin                                                                    0.73       1.0                                              Kathon CG         0.001      --                                               Bronopol          --         0.02                                             Distilled Water   Balance    Balance                                          ______________________________________                                    

Example III

The ingredients of Example III are mixed and dissolved into a clearsolution. Methylated alpha-cyclodextrin and methylated beta-cyclodextrinare obtained as a mixture from the methylation reaction of a mixture ofalpha-cyclodextrin and betacyclodextrin.

Example IV

The ingredients of Example IV are mixed and dissolved in a vessel into aclear solution.

    ______________________________________                                                           Example V Example VI                                       Ingredients        Wt. %     Wt. %                                            ______________________________________                                        alpha-Cyclodextrin 0.5       --                                               Hydroxypropyl-beta-cyclodextrin                                                                  0.5       1.0                                              Kathon CG          0.0005    0.001                                            Distilled water    Balance   Balance                                          ______________________________________                                    

Examples V and VI

The ingredients of Examples V and VI are mixed and dissolved into clearsolutions. The hydroxypropyl-beta-cyclodextrin has a degree ofsubstitution of about 5.0

    ______________________________________                                                          Example VII                                                                              Example VIII                                     Ingredients       Wt. %      Wt. %                                            ______________________________________                                        Alpha-cyclodextrin                                                                              0.5        --                                               Hydroxypropyl-alpha-cyclo-                                                                      --         0.27                                             dextrin                                                                       Hydroxypropyl-beta-cyclodextrin                                                                 0.5        0.73                                             Propylene glycol  0.01       0.06                                             Kathon CG         0.001      0.0008                                           Distilled water   Balance    Balance                                          ______________________________________                                    

Example VII

The ingredients of Example VII are mixed and dissolved in a vessel intoa clear solution. The hydroxypropylobeta-cyclodextrin has a degree ofsubstitution of about 5.4.

Example VIII

The ingredients of Example VIII are mixed and dissolved into a clearsolution. Hydroxypropyl alpha-cyclodextrin and hydroxypropylbeta-cyclodextrin are obtained as a mixture with an average degree ofsubstitution of about 4.9, from the hydroxypropylation reaction of aminute of alpha-cyclodextrin and beta-cyclodextrin. Propylene glycol isa minor by-product (about 6%) of the same reaction.

    ______________________________________                                                           Example IX Example X                                       Ingredients        Wt. %      Wt. %                                           ______________________________________                                        alpha-Cyclodextrin 0.5        --                                              beta-Cyclodextrin  1.0                                                        Hydroxypropyl-alpha-cyclodextrin                                                                 --         1.0                                             Hydroxypropyl-beta-cyclodextrin                                                                  --         2.5                                             gamma-Cyclodextrin 0.5        1.0                                             Kathon CG          0.001      0.001                                           Distilled water    Balance    Balance                                         ______________________________________                                    

Examples IX and X

The ingredients of Examples IX and X are mixed and dissolved into clearsolutions.

    ______________________________________                                                           Example XI Example XII                                     lngredients        Wt. %      Wt. %                                           ______________________________________                                        alpha-Cyclodextrin 0.5        --                                              Methylated beta-cyclodextrin                                                                     0.5        --                                              Hydroxypropyl alpha-cyclodextrin                                                                 --         0.27                                            Hydroxypropyl beta-cyclodextrin                                                                  --         0.73                                            Zinc chloride      1.0        1.0                                             Kathon CG          0.0008     0.0008                                          Propylene glycol   --         0.06                                            HCl                (a)        (a)                                             Distilled water    Balance    Balance                                         ______________________________________                                         (a) To adjust solution pH to about 4.8                                   

Example XI

About 5 parts of alpha-cyclodextrin and about 5 parts of methylatedbeta-cyclodextrin are added with mixing in a vessel containing about 980parts of distilled water. When the cyclodextrins are totally dissolvedinto a clear solution, about 10 parts of zinc chloride is added withmixing. Zinc chloride is dissolved into a milky white solution. Thesolution is adjusted to about pH 4.8 with a very small amount ofhydrochloric acid, upon which the solution becomes clear again. Thenabout 0.67 part of a nominally 1.5% aqueous solution of Kathon CG isadded with mixing until the solution becomes water clear.

Example XII

The composition of Example XII is prepared similarly to that of ExampleXI.

    ______________________________________                                                          Example XIII                                                                              Example XIV                                     Ingredients       Wt. %       Wt. %                                           ______________________________________                                        beta-Cyclodextrin 0.8         --                                              Hydroxypropyl beta-cyclodextrin                                                                 --          1.0                                             Zinc chloride     1.0         --                                              ZnSO.sub.4.7H.sub.2 O                                                                           --          2.2                                             Kathon CG         0.0008      0.0008                                          Propylene glycol  --          0.05                                            HCl               (a)         (a)                                             Distilled water   Balance     Balance                                         ______________________________________                                         (a) To adjust solution pH to about 4.8                                   

Examples XIII and XIV

The composition of Examples XIII and XIV are prepared similarly to thatof Example XI.

What is claimed:
 1. A stable, aqueous odor absorbing fabric treatingcomposition, comprising:A. from about 0.1% to about 1.85% ofsolubilized, uncomplexed beta-cyclodextrin; B. aqueous carrier; C. aneffective amount for preserving said composition, of a water-soluble,antimicrobial preservative having a water-solubility of greater thanabout 0.3% at room temperature; andwherein said composition isessentially free of any material that would soil or stain fabric; andwherein said composition is essentially free of perfume and has a pH ofgreater than about
 3. 2. The composition of claim 1 additionallycomprising cyclodextrin selected from the group consisting ofalpha-cyclodextrin, gamma-cyclodextrin, and derivatives of alpha-,beta-, and gamma-cyclodextrin, and mixtures thereof, the total amount ofcyclodextrin being less than about 5%.
 3. The composition of claim 1wherein said cyclodextrin is alpha-cyclodextrin, derivatives of alpha-and beta-cyclodextrin, or mixtures thereof.
 4. The composition of claim1 wherein said preservative is an organic sulfur compound selected frownthe group consisting of 5-chloro-2-methyl-4-isothiazolin-3-one;2-n-butyl-3-isothiazolone; 2-benzyl-3-isothiazolone;2-phenyl-3-isothiazolone, 2-methyl-4,5-dichloroisothiazolone;2-methyl-4-isothiazolin-3-one; 5-chloro-2-methyl-3-isothiazolone; andmixtures thereof.
 5. The composition of claim 4 wherein saidpreservative is a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and2-methyl-4-isothiazolin-3-one present at a level of from about 0.0001%to about 0.01% by weight of the composition.
 6. The composition of claim1 wherein said preservative is a halogenated compound selected from thegroup consisting of 5-bromo-5-nitro-1,3-dioxane;2-bromo-2-nitropropane-1,3-diol; 1,1'-hexamethylenebis(5-(p-chlorophenyl) biguanide); and mixtures thereof.
 7. Thecomposition of claim 6 wherein said preservative is2-bromo-2-nitropropane-1,3-diol present at a level of from about 0.002%to about 0.1%, by weight of the composition.
 8. The composition of claim1 wherein said preservative is a cyclic organic nitrogen compoundselected from the group consisting of imidazolidinedione compounds,polymethoxy bicyclic oxazolidine, and mixtures thereof.
 9. Thecomposition of claim 1 wherein said cyclodextrin is present at a levelof from about 0.2% to about 1.85%, by weight of the composition and saidpreservative is present at a level of from about 0.0001% to about 0.5%,by weight of the composition.
 10. The composition of claim 9 whereinsaid cyclodextrin is present at a level of from about 0.3% to about1.85%, by weight of the composition and said preservative is present ata level of from about 0.0002% to about 0.2%, by weight of thecomposition.
 11. The composition of claim 10 wherein said cyclodextrinis present at a a level of from about 0.5% to about 1.85%, by weight ofthe composition and said preservative is present at a level of fromabout 0.0003% to about 0.1%, by weight of the composition.
 12. Thecomposition of claim 1 additionally comprising from about 0.1% to about10%, by weight of the composition, of a metallic salt selected from thegroup consisting of water-soluble zinc salts, water-soluble coppersalts, and mixtures thereof.
 13. The composition of claim 12 whereinsaid metallic salt is selected from the group consisting of ZnCl₂,CuCl₂, and mixtures thereof.
 14. The composition of claim 13 whereinsaid metallic salt is ZnCl₂ present at a level of from about 0.1% toabout 10%, by weight of the composition.
 15. The method of treatingfabric comprising spraying an effective amount, for controlling odor, ofthe composition of claim 1 onto fabric with a trigger-spray devicehaving a bottle comprising clear polyethyleneterephthalate.
 16. A clear,stable, aqueous odor absorbing fabric treating composition,comprising:A. from about 0.5% to about 5%, by weight of the composition,of a mixture of alpha-cyclodextrin and beta-cyclodextrin: B. from about0.0001% to about 0.01%, by weight of the composition, of solubilized,water-soluble, antimicrobial preservative comprising a mixture of5-chloro-2-methyl-4-isothiazolin-3-one and2-methyl-4-isothiazolin-3-one; and C. water; andwherein said compositionis essentially free of any material that would soil or stain fabrics;and wherein said composition is essentially free of any perfume, and hasa pH of greater than about
 4. 17. A clear, stable aqueous odor absorbingfabric treating composition, comprising:A. from about 0.3% to about1.85%, by weight of the composition, of beta-cyclodextrin; B. from about0.0001% to about 0.01%, by weight of the composition, of solubilized,water soluble, antimicrobial preservative comprising a mixture of5-chloro-2-methyl-4-isothiazolin-3-one and2-methyl-4-isothiazolin-3-one; and C. water; andwherein said compositionis essentially free of any material that would soil or stain fabric; andwherein said composition is essentially free of any perfume and has a pHof greater than about
 4. 18. A clear, stable, aqueous odor absorbingfabric treating composition, comprising:A. from about 0.1% to about 5%,by weight of the composition, of a mixture of hydroxypropylbeta-cyclodextrin and hydroxypropyl alpha-cyclodextrin; B. from about0.0001% to about 0.01%, by weight of the composition, of solubilized,water-soluble, antimicrobial preservative comprising a mixture of5-chloro-2-methyl-4-isothiazolin-3-one and2-methyl-4-isothiazolin-3-one; and C. from about 0.3% to about 5%, byweight of the composition, of ZnCl₂ ; and D. water; andwherein saidcomposition is essentially free of any material that would soil or stainfabric; and wherein said composition is essentially free of any perfumeand has a pH of from about 4 to about 5.5.